Process for the manufacture of insoluble azo dyestuffs on cellulose fibers

ABSTRACT

Process for the preferably continuous manufacture of waterinsoluble azo dyestuffs on textile materials made of cellulose fibers, which comprises carrying out, after the application of the coupling component and of the diazo component from an aqueous dye bath, the finishing operation of the dyeings in organic solvents. The diazo component is in the form of a diazo-amino compound capable of being split up or of an anti-diazotate of a primary aliphatic amine. The organic solvent a hydrocarbon which may be halogenated, aromatic or cycloaliphatic.

United States Patent 1191 "Liiwcnfeld, Rudolf Jan.- 22, 1974 [54] PROCESS FOR IHE MANUFACTURE OF 2,274,751 3/1942 Sowter et al 8/173 INSOLUBLE zo DYESTUFFS'ON 2,l73,l78 9/1939 Moncrieff et al. 8/48 CELLULOSE FIBERS [75] Inventor: Liiwenield, Rudolf, Buchschlag, p a E i |d L Germany Assistant Examiner-Bruce H. Hess [73] Assign, Farbwerke Hoechst Attorney, Agent, or FirmHenry W. Koster et al.

Aktiengesellschait vormalsMeister Lucius 8: Brunmg' Frankfurt am 'MQEEFEWQHX 57 ABSTRACT [2 Filed: Dec. 10, 1971 [211 App]. 206,904 Process for the preferably continuous manufacture of v water-insoluble azo dyestuffs on textile materials made of cellulose fibers, which comprises carrying out, after Foreign App c Data the application of the coupling component and of the Dec. 12, I970 Germany 2061357 diazo component from an aqueous dye bath, the finishing operation of the dyeings in organic solvents. [52] US. Cl. 8/45, 8/71 The diazo component is in the fonn of a diazo-amino [51] Int. Cl. D06p 1/12, C09b. 27/00 compound capable of being split up or of an anti- [58] Field ot Search 8/44,-45, 7l diazotate of a primary aliphatic amine. The organic solvent a hydrocarbon which may be halogenated, ar- [56] References Cited omatic or 'cycloaliphatic.

UNITED STATES PATENTS 3 Claims, No Drawings PROCESS FOR THE MANUFACTURE OF INSOLUBLE AZO DYESTUFFS ON CELLULOSE FIBERS The present invention relates to a process for the dyeing .of Cellulose fibers which permits to reduce the water consumption as compared to conventional processes to a large extent and thus to avoid the problems of eliminating the sewage .water.

'According to the known methods of the ice-colourtechnique, insoluble azo dyestuffs are manufactured in a continuous manner on woven or knitted fabrics or cellulose fibers such that the material to be dyed is first impregnated with the aqueous, alkaline solution of a coupling component, dried and then 'treated with the aqueous, slightly acidic solution of a diazo component. According to this process the dyestuff is formed when the material to be dyed passes through the solution of the diazo component or during the subsequent passage three to eight baths continuously with hot, organic solvents. The dyestuff pigments formed on the ceelulose fiber should have a limited solubility in the solvents used. In the organic solvents used according to this process, slight amounts of water may also be emulsified if necessary. Finally, the dyeling produced is dried and the solvent recovered.

According to this invention, a mode of proceeding especially simplifying the dyeing is possible if the insoluble azo dyestufi is manufactured from the coupling component and the diazo-amino compound or the antidiazotate of a primary aromatic amine. In such a case, release of the diazonium compound capable of coupling which is mandatory before the dyestuff coupling may be carried out in the hot solvent, to which an organic acid miscible with the corresponding solvent is added for this purpose. In the course of the said emof the treated goods through the air. After coupling,

the material is first passed through aqueous rinsing baths and the dyeing is then treated for being finished with alkaline, aqueous solutions containing detergents at the boiling temperature. Finally, the dyed articles are dried.

Insoluble azo dyestuffs may also be manufactured on cellulose fibers in such a manner that in the aqueous, alkaline solution of a coupling component the diazoamino compound of a primary aromatic amine is simultaneously dissolved, both components are applied together to the material by impregnation and the dyestuff formation is achieved by treating the textile material thus impregnated with an acid which is diluted with water, by acidic steaming or by exposing it to the effect of dry heat with or without the addition of acidyielding agents. Then, the dyeing is finished by rinsing and aftertreating in aqueous baths and finally dried.

In these known dyeing processes important amounts of water are used especially for rinsing and aftertreating purposes. Furthermore, drying of the material requires a high amount of energy for'the evaporation of the water. Due to the considerable volume the high water consumption in practicefor finishing the dyeings raises, from the technical point of view, more or less big problems with regard to the clarification of sewage waters, according to the local conditions, which is of great disadvantage for the rentability of these processes.

Now, it was found that in the preferably continuous manufacture of water-insoluble azo dyestuffs on textile materials made of cellulose fibers the water consumption and, thus, the amount of sewage water resulting in the total dyeing process may be reduced to a minimum when, after the application of the coupling component and of the diazo component from an aqueous dyebath, the finishing operation of the dyeings is carried out in organic solvents.

According to the operational steps for carrying out the process of the invention, the textile material, for example, a fabric web, is impregnated with the aqueous, alkaline solution of a coupling component, dried and passed through the aqueous solution of a diazonium compound capable of coupling which liquor contains alkali-binding agents inthe form of a voltatile, organic acid. The dyeing obtained is then treated in the moist or dried state by means of a passage through bodiment, the coupling component and the diazo component in form of a diazoamino compound capable of being split up or of an anti-diazotate are applied in aqueous, alkaline solution to a fabric web at the same time. Then, the impregnated material is passed in the moist or dried state through three to eight baths with hot, organic solvents, the first bath thereof containing an addition of a volatile, organic acid.

As it has proved on the basis of the operating methods described above, the water consumption in the dyeing and finishing of the dyeings according to the invention is reduced to a minimum as compared to the water amounts which are required in the manufacture of corresponding insoluble azo dyestuffs on cellulose fibers according to known processes.

To. carry out the process of the invention coupling components are used which have a slight to medium substantivity towards the textile material. As such substances, there may be mentioned: the arylides of the B-hydroxy-naphthoic acid, for example 2,3-hydroxynaphthoic acid anilide, l-( 2 3"-hydroxy-naphthoyl-amino)-2-methoxy-benzene, 1-(2',

3 'hydroxy-naphthoyl-amino-2-methyl-4- chlorobenzene, 1-(2-, 3'-hydroxy-naphthoyl-amino)- 2,4-dimethoxy-5-chlorobenzene or l-(2', 3-hydroxy-naphthoyl-amino)-3-nitrobenzene:

the arylides of the 6-methoxy-2,3-hydroxy-naphthoic acid, for example, 6-methoxy-2,3-hydroxy-naphthoic acetoacetyl-amino compounds, for example, 4,4-bisacetoacetylamino-3.3'-dimethyl-diphenyl; or

chloroanilines, chlorotoluidines, anisidines, chloroanisidines, trifluoromethyl-anilines, nitroanilines, ni trotoluidines, nitroanisidines, aminophenyl-sulfonic acid amides, aminophenyl-carboxylic acid amides, aminodiphenyl ethers, aminoazobenzenes, N- substituted phenylene diamines, diamino-diphenyls or amino-anthraquinones.

Suitable alkalis used for the dissolution of the coupling component, are aqueous sodium hydroxide solution, aqueous potassium hydroxide solution or strong organic bases, for example, ethyl-diethanol-amine. As protective colloides in the alkaline impregnation bath, there may be used albumen condensation products, sulfonated castor oils, condensation products of naphthalene sulfonic acids with formaldehyde or condensation products from oleic acid with N-methyl-taurine.

As acidic agents in the aqueous solutions of diazonium compounds or as acidic additive to organic solvents to set free the diazonium compounds capable of coupling from the diazoamino compounds or antidiazotates which can be used in accordance with the invention, there are mentioned volatile, organic acids, for example, acetic acid, formic acid or propionic acid.

As organic solvents, there may be used in the present invention, in pure form, in mixture with one another, or in emulsion by the addition of up to 6% of water:

halogenated hydrocarbons, for example, trichloroethylene, perchloroethylene, tetrachloroethane, methylene chloride, or trifluorotrichloroethane; aromatic hydrocarbons, for example, benzene or xylene; and aliphatic or cycloaliphatic hydrocarbons, for example, Tetralin.

The following Examples illustrate the invention, the

4 ture of from 60 to 120C. Finally, the dyed material was dried and the solvent was recovered. An intense red dyeing was obtained having good fastness properties.

When carrying out the above dyeing, from I.- 5% of water may be emulsified in the perchloroethylene baths. Instead of perchioroethylene, there may also be used as treating liquid trichloroethylene, tetrachloroethane, xylene, Tetralin of fluorinated hydrocarbons. The treating temperature depends on the boiling points each of the solvents.

Composition of Solution A Fifteen g of l-(2.3-hydroxy-naphthoyl-amino)-2- methoxybenzene were dissolved by boiling in a mixture of 15 cc. of sodium hydroxide solution (of 32.5%) and l l of soft water. and 3 g of a condensation product form naphthalene sulfonic acid and formaldehyde were added to this solution.

N Composition of Solution B 13.5 g of the sulfate of 1-amino-2,5-dichlorobenzene were diazotized by pouring over 27 cc. of hydrochloric acid (of 32%), 27 cc of water and ice as well as an aqueous solution of 10 g of sodium nitrite, the clear diazo solution was then introduced in a bath of l l of cold water which contained 2 g of a condensation product from 1 mol of octadecyl alcohol with 10 mols of ethylene oxide, 34 g of crystallized sodium acetate and 15 cc. of acetic acid (of The following Table 1 shows further combinations of coupling components and diazo components by means of which also intense dyeings of good fastness properties may be manufactured according to the process of this inveniton.

TABLE I Coupling component diazo component Shade 2,3-hydroxynaphthoic acid anilide l-( 2' ,3 '-hydroxynaphthoylamino)-2-methyl-4-chlorobenzene l-( 2' ,3 '-hydroxynaphthoylamino)-2,4-dimethoxy-S-chlorobenzene 1-amino-2-methyl-5-nitrobenzene l-amino-2-methyl4-chlorobenzene scarlet red red l-amino-2-methoxybenzene-5-diethylsulfonic acid amide 6-methoxy-2,3-hydroxynaphthoic acid anilide l-(2', hydroxycarbazole-3'-earboylamino )4-chlorobenzene 4,4'-bis-acetoacetylamino-3,3-dimethyl-diphenyl 2-(2', 3'-hydroxynaphthoylamino)-naphthalene l-(S, hydroxy-l,2',l", 2"-benzocarbazole-4'-carboyl-amino)-4-methoxy benzene 2,3-hydroxynaphthoic acid anilide 2,3-hydroxynaphthoic acid anilide 2.3-hydroxynaphthoic acid anilide 2,3-hydroxynaphthoie acid anilide parts and percentages being by weight, unless stated otherwise.

EXAMPLE 1 A cottom fabric was continuously passed through the Solution A heated to 60-90C and having the composition indicated hereinafter, and was squeezed between rolls to yield a liquor absorption of 80%, calculated on l-amino-3-chlorobenzene l-amino-2-methoxy-4-nitrobenzene l-amino-2-methyl-3-chlorobenzene l-amind-2-methyl-5-chlorobenzene l-amino-2-methoxy-4-nitrobenzene 4-amino-2',3-dimethyll l '-azobenzene 4-amino-4'-methoxydiphenyl amine l-arnin0-2,4-dimethoxy-4-benzoyl-aminobenzene 4,4'-diamino-3,3-dimethoxy-diphenyl the weight of the dry material. THe padded fabric was then dried by means of hot air at l00-l20C, passed through the cold Solution B having the composition hereinafter described and was again squeezed between rolls to yield a liquor absorption of 80%. Subsequently, the padding was exposed to the action of air at room temperature for 30-60 seconds and then passed through two to five perchloroethylene baths at a tem'peraclaret brown yellow red black garnet blue blue blue dium cyanamide, dissolved by pouring over hot water of 70C.

After impregnation, the material was squeezed between rolls to yield a liquid absorption of 80%, calculated on the weight of the dry material, dried and passed through a bath of trichloroethylene heated to 80C which contained 3 cc./l of acetic acid (of 100%). Thematerial should be exposed to the efiect of the acetic solvent bath for at least seconds. In two to five subsequent baths of trichloroethylene heated to 60 to 80C the dyeing obtained was rinsed and finished. An intense red dyeing was obtained. Finally, the dyed fabric was dried and the solvent was recovered.

When carrying out the above dyeing, from 1 5% of water may be emulsified in the organic treating baths. Instead of trichloroethylene there may also be used perchloroethylene, methylene chloride or fluorinated hydrocarbons as treating liquid. The treating temperatures depend each time on the boiling points of the solvents.

The following Table II shows further combinations of coupling components and diazo components in the form of their diazo-amino compounds or anti- We claim:

1. In a process for the preferably continuous manufacture of water-insoluble az'o dyestuffs on textile materials made of cellulose fibers by impregnating said fibrous materials with an aqueous-alkaline liquor of a coupling component and a diazo-amino compound capable of being split up or an antidiazotate of a primary aromatic amine, and causing development of the dyestuff on the fiber, the improvement which comprises: passing the impregnated goods in .the water-moist or dried state through a bath of an organic solvent maintained at a temperature of from 60 to 120C, said solvent being selected from the group consisting of trichloroethylene, perchloroethylene, tetrachloroethane, methylene chloride, trifluorotrichloroethane, benzene, xylene and l, 2, 3, 4, tetrahydronaphthalene and containing a volatile organic acid, miscible therewith, to set free the diazonium compound capable of coupling and for the subsequent coupling reaction and the finishing operation.

2. A process as claimed in claim 1, wherein the dyestuff pigments obtained show a limited solubility in the solvent used.

TABLE II Coupling component diazo-amino compound (DA) or antidiazotate Shade l-(2,3'-hydr0xy-naphthoyl-amino)-2-methoxy-benzene DA from diazotized bluish red l-amino-Z-methoxy-S-chlorobenzene and sodium N-methyl-amino acetate 1-(2,3'-hydroxynaphthoylamino)-2-methyl-benzene DA from diazotized yellowish red l-amino-Z-methyl-S-chlorobenzene and sodium cyan-amide 4,4'-bis-acetoacetylamino-3,3'-dimethyl-diphenyl DA from diazotized yellow l-amino-Z-methyl-S-chlorobenzene and sodium N-methyl-amino acetate 142', DA from diazotized blue 3'-hydroxynaphthoylamino)-2-methyl-4-chlorobenzene 4,4-diamino-3,3' -dimethoxy-diphenyl and N-methyltaurine 2-(2',3'-hydroxynaphthoylarnino)-naphthalene DA from diazotized blue l-amino-2,5-diethoxy-4-benzoylaminc-benzene and sodium N-methvlamino acetate l-(2,3'-hydroxynaphthoylamino)-2.4-dimethoxy-5- DA from diazotized l-amino-2-methyl-3- dull bluish red chlorobenzene chlorobenzene and sodium cyanamide l-(2',3'-hydroxynaphthoylamino)-2-methoxy-4-chloro-5- AN from diazotized l-amino-Z-methoxy-S- bluish red methyl-benzene chlorobenzene l-(2',3'-hydroxynaphthoylamino)-2-methoxybenzene AN from diazotized l-amino-Z-chloro-S- yellowish red trifluoromethyl benzene l(2'-hydroxycarboazole-3-carboylamino)-4-chloro- DA from diazotized l-amino-Z-methyl-S- brown benzene chloro-benzene and sodium cyanamide l-(S-hydroxy-l',2.l",2"-benzocarbazole 4'- DA from diazotized l-amino-2-methoxy-4- black carboylamino)-4-methoxybenzene nitrobenzene and sodium cyanamide 4,4-bisacetoacetylamino-3.3'-dimethyl-diphenyl DA from l-amino-2-methyl-5-chloroyellow benzene and sodium cyanamide 2,3-hydroxynaphthoylamino-benzene DA from diazotized l-amino-Z-methyl-S- red chloro-benzene and sodium cyanamide 2,3-hydr0xynaphthoylamino-benzene DA from diazotized l-amino-2-diethoxy-4- blue diazotates by means of which also intense dyeings of good fastness properties can be obtained according to vent used contains up to 6% of emulsified water.

this invention. a

benzoyl-amino-benzene and sodium N-methylammo-acetate 3. A process as claimed in claim 1, wherein the sol- 

2. A process as claimed in claim 1, wherein the dyestuff pigments obtained show a limited solubility in the solvent used.
 3. A process as claimed in claim 1, wherein the solvent used contains up to 6% of emulsified water. 